Production of polyesters

ABSTRACT

AN IMPROVED MULTIFILAMENT POLYETHYLENE TEREPHTHALATE YARN HAVING A LUBRICATING PROTECTIVE FILM APPLIED THEREON OF FROM ABOUT 0.3 TO ABOUT 0.6 WEIGHT PERCENT BASED ON THE WIGHT OF THE YARN OF A LIQUID COMPOSITION CONSISTING ESSENTIALLY OF ABOUT 10 TO ABOUT 20 WEIGHT PERCENT OF SAID COMPOSITION OF EACH HEXADECYL STEARATE AND REFINED COCONUT OIL, ABOUT 3.0 TO ABOUT 6.0 WEIGHT PERCENT OF SAID COMPOSITION OF ETHOXYLATED TALLOW AMINE, ABOUT 10 TO ABOUT 20 WIGHT PERCENT OF SAID COMPISTION OF ETHOXYLATED LAURYL ALCOHOL, ABOUT 8.0 TO ABOUT 12.0 WEIGHT PERCENT OF SAID COMPOSITION OF SODIUM SALT OF ALKYLARYLSULFONATE, ABOUT 1.0 TO ABOUT 3.0 WEIGHT PERCENT OF DINONYLSODIUM-SULFOSUCCINATE, ABOUT 1.0 TO ABOUT 3.0 WIGHT PERCENT OF SAID COMPOSITION OF 4,4&#39;&#39;-THIO-BIS-(3-METHYL-6-TERTBUTYLPHENOL), ABOUT 35 TO 50 WEIGHT PERCENT OF SAID COMPOSITION OF WHITE MINERAL OIL HAVING A BOILING POINT OF BETWEEN 510*F. AND 620*F. WHEREIN AT LEAST ABOUT 0.15 TO ABOUT 0.30 WEIGHT PERCENT IS RETAINED ON SAID YARN, AND THEN TREATING SAID YARN WITH FROM ABOUT 0.7 TO ABOUT 1.2 WEIGHT PERCENT ON SAID YARN OF A LIQUID COMPOSITION SELECTED FROM THE GROPU CONSISTING OF (A) ABOUT 95 TO ABOUT 98 WEIGHT PERCENT OF SAID COMPOSITION OF TRIETHYLENE GLYCOL-DIPELARGONATE AND ABOUT 2 TO ABOUT 5 WEIGHT PERCENT OF SAID COMPOSITION OF 2,2&#39;&#39;METHYLENE-BIS-(4METHYL-6-TERT NONYLPHENOL), AND (B) ABOUT 13 TO ABOUT 25 WEIGHT PERCENT OF SAID COMPOSITION SELECTED FROM THE GROUP CONSISTING OF GLYCEROL MONOLEATE AND DECAGLYCEROL TETRAOLEATE WITH ETHOXYLATED TALL OIL FATTY ACIDS, ABOUT 12 TO ABOUT 20 WEIGHT PERCENT OF SAID COMPOSITION SELECTED FROM THE GROUP CONSISTING OF SULFATED GLYCEROL TRIOLEATE AND ETHOXYLATED ALKYLAMINE, AND ABOUT 55 TO ABOUT 75 WEIGHT PERCENT OF SAID COMPOSITION OF HEXADECYL (ISOCETYL) STEARATE.

United States Patent 3,672,977 PRODUCTION OF POLYESTERS KimonConstantine Dardoufas, Richmond, Va., assignor to Allied ChemicalCorporation, New York, N.Y. No Drawing. Filed Oct. 26, 1970, Ser. No.84,168 Int. Cl. C083 1/44; D06m 13/00 US. Cl. 117138.8 F 1 ClaimABSTRACT OF THE DISCLOSURE An improved multifilament polyethyleneterephthalate yarn having a lubricating protective film applied thereonof from about 0.3 to about 0.6 weight percent based on the weight of theyarn of a liquid composition consisting essentially of about 10 to about20 weight percent of said composition of each hexadecyl stearate andrefined coconut oil, about 3.0 to about 6.0 weight percent of saidcomposition of ethoxylated tallow amine, about 10 to about 20 weightpercent of said composition of ethoxylated lauryl alcohol, about 8.0 toabout 12.0 weight percent of said composition of sodium salt ofalkylarylsulfonate, about 1.0 to about 3.0 weight percent ofdinonylsodium-snlfosuccinate, about 1.0 to about 3.0 weight percent ofsaid composition of 4,4-thio-bis-(3-methyl-6-tertbutylphenol), about 35to 50 weight percent of said composition of white mineral oil having aboiling point of between 510 F. and 620 F. wherein at least about 0.15to about 0.30 weight percent is retained on said yarn, and then treatingsaid yarn with from about 0.7 to about 1.2 weight percent on said yarnof a liquid composition selected from the group consisting of (a) about95 to about 98 weight percent of said composition of triethyleneglycol-dipelargonate and about 2 to about 5 weight percent of saidcomposition of 2,2'-methylene-bis-(4- methyl-6-tert nonylphenol), and(b) about 13 to about 25 Weight percent of said composition selectedfrom the group consisting of glycerol monoleate and decaglyceroltetraoleate with ethoxylated tall oil fatty acids, about 12 to about 20weight percent of said composition selected from the group consisting ofsulfated glycerol trioleate and ethoxylated alkylamine, and about 55 toabout 75 weight percent of said composition of hexadecyl (isocetyl)stearate.

BACKGROUND OF THE INVENTION This invention relates to improvedmultifilament yarns, and particularly to multifilament polyethyleneterephthalate yarns for industrial uses. More particularly it relates toa new finishing process for polyester yarns in which novel finishcompositions are applied to said yarns.

Synthetic continuous filament yarns are produced wherein lubricatingcompositions containing antistatic properties are applied in order tomeet processing requirements and particularly at high speeds. As greaterrequirements are made on the physical properties of such yarns in lightof new and improved safety regulations with respect to their ultimateend use, the compositions must contain materials, for example, as yarnto cord conversion efiiciency, cord to rubber adhesion, improved fatigueproperties, improved thermal stability, etc. In known prior practice ofutilizing a one step finish, that is, a spin finish which would supportan eflicient fiber process performance while at the same time wouldprovide the desired tire cord properties, a compromise must always beaccepted between fiber process efiiciency and tire yarn surfacerequirements.

Accordingly, it is an object of this invention to provide an improvedpolyester continuous filament yarn and an improved process for preparingsaid yarn. A further object of this invention is to provide an improvedpolyester filament yarn and an improved process for preparing said yarnfor reinforcing rubber tires, by using first, an improved compositionfor use as a process finish, followed by an improved composition for useas yarn to yield the desired yarn cord properties.

Polyester yarns are known to be drawn at elevated temperatures anthermal variability depends upon the thermodynamic properties of thefinish which effects processing performance as well as yarn physicalproperties. Therefore, parameters such as low finish specific heat and,low heat of vaporization of the volatile components and the lowestfinish level required for fiber protection are essential to minimizeheat losses for good fiber processing performance. This illustrates theinferior performance of all aqueous finishes in comparison to thenonaqueous finishes which can be applied at a level significantly lowerfor the same or equivalent percent solids on yarn and have much lowerspecific heat and heat of vaporization compared to aqueous or water basematerial.

The improved composition for use as the process finish in accordancewith this invention consists of a non-aqueous homogeneous blend oflubricants; emulsifiers, antistat, wetting agent; and, an antioxidant.The blend is a clear liquid free of suspended solids, and having aviscosity of 27 centipoises at room temperature, a surface tension ofabout 32 dynes per centimeter and a contact angle on polyester of about9, which insures proper wetting ability for uniform distribution of thecomposition. The lubricating and continuous phase of the compositionconsists of about 39 weight percent mineral oil of low viscosity ofabout 40 SSU at F., flash point of 260 F., and boiling range of about510 F. to 620 F., about 14.5 weight percent coconut oil and 14.5 weightpercent hexadecyl steara-te which have low volatility and excellent heatsta-v bility. The remainder consists of about 10 Weight percent ofnatural petroleum sulfonate (sodium salt of alkylarylsulfonate) which isan excellent emulsifier and antistat due to its high ionization, about 5weight percent of ethoxylated (20 ETO) tallow amine which is anexcellent emulsifier and antistat, about 13 Weight percent ofethoxylated (4 ETO) lauryl alcohol emulsifier coupling agent, about 2weight percent of sodium salt of nonyl sulfosuccinate which is anexcellent wetting agent, and 2 weight percent of an antioxidant4,4-thio-bis-(6-tert butyl mlcresol).

The processfinish composition is applied onto the yarn in such a way asto allow about 0.3 to about 0.6 weight percent of said composition to beinitially applied and with from about 0.15 to about 0.30 weight percentretained on the yarn to protect the fiber surface, required lubricity,and antistatic properties. During the heat treatment of the yarnsubsequent to the application of the process finish composition, about40 to about 50 weight percent of the composition is volatilized. Thevolatiles consist mainly of the low viscosity mineral oil which containsa very low level of the other necessary components. The volatiles arecondensed and can be recovered through an exhaust system. The remainingprocess finish composition provides adequate surface lubrication,antistatic properties and antioxidant to protect the yarn surface duringthe subsequent drawing operation. An excellent advantage of this processfinish composition is that even when exposed to extremely hightemperatures as required in a polyester spin draw or conventionalspinning and drawing process, it suffers substantially no decomposition,thus preventing possible deposits on processing rolls and otherthreadpath components that affect processing efficiency.

The process finish composition is unique not only due to its compositionwhich provides all requirements of lubrication, antistatic propertiesand protection from heat degradation, but because of its followingphysical properties which are essential or critical for uniformity ofapplication and efiicient fiber thermal treatment. First, low

viscosity of less than 40 centipoises at 25 C. by Brookfield Viscometer,for application at room temperature is critical. Second, good wettingability measured by contact angle method on polyester film is necessary.A contact prove its translational efficiency of yarn to tensilized cord,adhesion, heat stability, fatigue and tire durability properties. Theyarn or ovenfinish composition can be applied construed as limitative.

TABLE I-FINISH COMPOSITIONS Finish compositions, parts by weight Finishidentities- A B O D E F G H I K L Function Finish components:

Refined coconut g1yceride 15. 30.0 14. 7 14. 5 18. 0 Lubricant.Hexadecyl (isocetyl) stearate 15. 0 14. 7 14. 5 19. 0 Do. Ethoxylatedlauryl alcohol (4 E0 13.0 13.0 12.7 12. 7 Emulsifier. Sodium petroleumsulionate 60-62% active in mineral oi 10.0 10. 0 9. 8 9. 7 Antistatemulsifier. Ethoxylated tallow amine (20 E0) 6.0 5.0 4.9 4. 9 10.0 Do.Sodium salt of sulfonated succinic ester 2. 0 2. 0 2. 0 1. 9 Wettingagent. Suliated glycerol trioleate 15. 0 Antistat emulsifier.Ethoxylated tallow acid (15 E0) Emulsifier. Decaglycerol tetraoieate Do.Glycerol monoleate Do. Ethoxylated sorbitol oleate-lanrate Do.Ethoxylated tallow glyceride o. Plastolein 9404 (triethylene glycoldipelargonate) 97. 0 Lubricant. Naugawhite(2,2-methylene-bis-(4-methyl-6-tert. nonylphenol) 3. 0 3. 0 3. 0 3. 0 3.0 Antioxidant. Santowhite crystals (4,4 thio-bis(6-tert.-butyl-mcreso2.0 0.6 0.7 0.7 Do. Triethylene glycol di-short chain fatty acids (0 -097. 0 35-6- LubJIJicant.

Neopentyl glycol di-pelargonate at any stage of the process subsequentto the critical drawing stage, thus yielding the unexpectedpossibilities of tailoring the surface properties of the fiber byadditives for improving adhesion, thermal stability, fatigue, etc.Either angle of less than 10 gives substantially ideal conditions 5 oneof two yarn finish compositions have been found to of finishspreadability. Third, the eight component spin be adequate in accordancewith this invention. process finish composition is a uniform blend,water clear, The improved yarn finish composition for use as the andfree of any suspended solids. In order to achieve this, overfinish oryarn finish compositions in accordance with an almost perfect HLB(hydrophylic-lipophylic balance) this invention consist of either (a)about 95 to about 98 is achieved without adverse eflects on any of theother 10 weight percent of said composition of triethyleneglycolessentiai properties of the finish composition. Just a minordipelargonate and about 2 to about 5 weight percent of variation ormodification of ratio of the composition insaid composition of2,2-methylene-bis-(4-methyl-6-tertiary gredients results in an unstableblend of cloudy appearance nonoylphenol) and (b) about 13 to about 25weight perwith suspended solids or complete separation of layers. centof said composition selected from the group consist- Fourth, thecomposition yields low specific heat and the 15 ing of glycerolmonoleate and decaglycerol tetraoleate lowest possible heat ofvaporization of the more volatile with ethoxylated tall oil fatty acids,about 12 to about components which provides good conditions to minimizeweight percent of said composition selected from the heat losses duringthe thermal treatment of the fiber. This group consisting of sulfatedglycerol trioleate and ethoxylimitation none of the more criticallimitations that aqu e l d lk l i d about 55 to about 75 i h 8 Z P F SIand 63111115121113 f c gti W111 20 cent of said composition of hexadecyl(isocetyl) stearate. e s own in e examp es w erem process con ons aswell as physical properties of the yarn cannot be obtained 6 yams ofthls mveimqn can be processed by f that are comparable to thisinvention. And, lastly, the Spm draw recess or spmmilg and separatelydrawing composition is heat stable when exposed to high process Processavallilble to m the patcnt technical temperatures and further, undergosubstantially no chemihteralure usuig any Suitable polyester whlchpiovldes cal degnadation even after partial volatilization or steam thehlgh tenacity Yam of about 9 grams Per demer and distillation. minimumelongation of about 13 percent.

yam finish or ovelifinish composition is applied The following examplesillustrate in Tables I, II, and onto the yam in such a way as to allowabout to I11, applicants present invention and advantages obtalned about1'2 Weight Percent to remain on Said yam to thereby by mterrelatmgfinish composmons to fiber process performance and end product of yarnand cord physical properties. They are illustrative only and are not tobe Wl/Iinteral oil viscosity 40 SSU 40. 0 40.0 39. 2 38. 8 Continuousphase.

a or

Physical state at room temp 1 Clear oil blend. 1 Hazy oil blend. 8Stable emulsion.

TABLE II.FIBER PROCESS PERFORMANCE DATA Fiber finish identity A B O O DE E F G H 0) Finish physical properties:

Viscosity in centipoises (Broolcfield) 22. 5 25. 0 29. 0 29. 0 26. 0 26.0 26. 0 7. 8 11. 0 9. 2 15. 6 Contact angles on polyester in degrees- 7.0 7. 0 4. 9 4. 9 7. 5 6. 2 6. 2 31. 0 30. 0 44. 0 8. 5 Surface tensionin dyn./cm 31. 7 31. 2 31. 8 31. 8 31. 5 31. 8 31. 8 36. 0 35. 5 36. 535. 0 Manufacturing performance:

Finish pick-up percent by wt. oi fiber 0. 0.45 0.45 2. 20 0. 45 0.45 1. 1. 3. 10 2. 1. 55 Finish oil on fiber by analysis, percent by wt-0. 2 0. 2 0. 2 1. 2 0. 2 0. 2 0. 8 0. 5 0. 7 0. 8 0. 7 Drawingperformance Exc. Exc. Exc. Fair Exc. Good Fair Fair Poor Poor Very badBreaks and wraps/1b.--- 0 0. 01 0 0. 09 0. 01 0. 04 0. 09 0. 07 0. 13 0.18 0. Y Depostisttlm draw heater None None Neg. Med. Neg. Slight HeavyMed. Med. Heavy Heavy am roper es:

Uitimate tensile strength, g.ld 8. 5 8. 5 8. 6 8. 5 8.4 8. 6 8. 5 8. 68. 5 8. 5 8. 3 Ultimate elongation at break, percent 14. 7 14.4 14. 614. 2 14. 2 14. 5 15.3 14. 2 14. 7 14. 1 15. 2 Yarn quality rating(broken filaments) 2 2 1 1 1 2 2 3 4 4 5 Yarn uniformity rating 4 1 1 13 1 l 3 4 5 5 4 Sample number 1 2 3 4 5 6 7 8 9 10 11 1 Clear oil. 1Hazy oil. l Aqueous emulsion. I Rating: 1=best, 5=worst.

TABLE III.YARN TIRE CORD PROPERTIES Fiber process finish identity C G AC A A Yarn over-finish identity G J K L Yarn sample identi 12 13 14 1516 17 Total finish oil on yarn, percent by wt .2 0.7 1.2 1.3 1.3 0.9Yarn:

Breaking strength in lbs 24.9 24.4 24.5 24.5 24.6 25.0 Percentelongation at break 13.0 13.9 13.3 12.8 12.9 13.1 Dipped tensilizedcord:

Breakingstrength in lbs 61.7 62.4 64.2 65.2 66.3 63.9 Percent elongationat break 13.1 14.7 15.2 15.3 16.1 15.4 Translational efiiciency, percent82.6 84.7 87.3 88.7 89.8 85.2 Thermal stability, pe ent e tained stren h81.7 75.5 79.3 79 80.3 77.8 Adhesion 3/8, hot- 32 83 32 36 33 30Adhesion 3/8, cold--- 40 46 41 43 42 44 Disk, fatigue, percent 65.8 68.083.4 76.5 80.2 77.6 Wheellife (hours) 79 60 104 98 84 N finish.

I claim:

1. Synthetic filamentary yarn comprised of polyethylene terephthalatefilaments which are first treated with from about 0.3 to about 0.6Weight percent based on the weight of the yarn of a liquid compositionconsisting essentially of about to about 20 weight percent of saidcomposition of each hexadecyl stearate and refined coconut oil, about3.0 to about 6.0 weight percent of said composition of ethoxylatedtallow amine, about 10 to about 20 weight percent of said composition ofethoxylated lauryl alcohol, about 8.0 to about 12.0 weight percent ofsaid composition of sodium salt of alkylarylsulfonate about 1.0 to about3.0 Weight percent of dinonyl-sodium-sulfosuccinate, about 1.0 to about3.0 weight percent of said composition of 4,4 thio-.bis-(3 methyl 6tert-butylphenol), about 35 to 50 weight per- 6 cent of said compositionof white mineral oil having a boiling point of between 510 F. and 620 F.and a viscosity of between 38 to 40 SSU at 100 F. wherein at least about0.15 to about 0.30 weight percent is retained on said yarn, and thensaid yarn is treated with from about 0.7 to about 1.2 weight percent onsaid yarn of a liquid composition selected from the group consisting of(a) about 95 to about 98 weight percent of said composition oftriethylene glycol-dipelargonate and about 2 to about 5 weight percentof said composition of 2,2 methylene bis (4 methyl 6 tert. nonylphenol),and (b) about 13 to about 25 weight percent of said composition selectedfrom the group consisting of glycerol monoleate and decaglyceroltetraoleate with eth oxylated tall oil fatty acids, about 12 to about 20weight percent of said composition selected from the group consisting ofsulfated glycerol trioleate and ethoxylated alkylamine, and about toabout weight percent of said composition of hexadecyl (isocetyl)stearate.

References Cited UNITED STATES PATENTS 3,428,560 2/1969 Olsen 117-1395 X3,563,892 2/1971 Cooley 1l7l38.8 X 3,575,856 4/1971 Anton 117.138.8 X

WILLIAM D. MARTIN, Primary Examiner T. G. DAVIS, Assistant Examiner US.Cl. XR.

117-76 T, 139.5 CQ, 139.5 F; 252-8.75, 8.8, 8.9

